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Acta Cryst. (2011). E67, o187    [ doi:10.1107/S1600536810052669 ]

rac-Diethyl 6-hydroxy-4-[(2-hydroxyethyl)amino]-6-methyl-2-phenylcyclohex-3-ene-1,3-dicarboxylate

A. M. Maharramov, A. I. Ismiyev and B. A. Rashidov

Abstract top

The title compound, C21H29NO6, is chiral with three stereogenic centres. The crystal is a racemate and consists of enantiomeric pairs with the relative configuration rac-(2R*,3S*,4R*). The ethyl fragment of the ethoxycarbonyl group at position 1 is disordered in a 0.60:0.40 ratio. The crystal packing displays intermolecular O-H...O hydrogen bonding. An intramolecular N-H...O hydrogen bond also occurs.

Comment top

β-Cycloketoles and their nitrogenous derivatives possess a wide spectrum of biological activity (Krivenko et al. 2003). The reactions of β-cycloketoles with ethanolamine possibly lead to valuable compounds of practical use but remain unexplored. Reaction β-cycloketoles with ethanolamine has not been studied. Several reaction paths may be expected: one or two reactive centres of the substrate and reagent may be involved. Enamines or the products of heterocyclisation or spirocyclisation may be produced.

The cyclohexene ring has a distorted half-chair conformation. Phenyl ring is in a pseudo-equatorial position (Fig. 1). Torsion angle between the ethoxycarbonyl group and the phenyl substituent, C12—C2—C3—C18 is 59,04 (18) °, indicating the pseudo-axial location of hydrogen atoms at C2 and C3. The crystal structure involves O—H···O intermolecular and O—H···O and N—H···O intramolecular hydrogen bonds (Table 1 and Fig. 2).

Related literature top

β-Cycloketoles and their nitrogenous derivatives possess a wide spectrum of biological activity, see: Krivenko et al. (2003).

Experimental top

(rac)-Diethyl-4-hydroxy-4-methyl-6-oxo-2-phenyl-1,3-dicarboxylate (20 mmol), monoethanolamine (20 mmol) were dissolved in 20 mL ethanol. The mixture was stirred at 345–350 K within 10 h. After cooling to a room temperature white crystals were obtained. The crystals were filtered and washed with ethanol. Then the crystals obtained were recrystallised from 50 mL ethanol to yield colourless block-shaped crystals of the title compound.

Refinement top

The hydrogen atoms of the NH and OH-groups of (I) were localized in the difference-Fourier map and included in the refinement with fixed positional and isotropic displacement parameters [Uiso(H) = 1.5Ueq(C) for CH3-group and Uiso(H) = 1.2Ueq(N) for amino groups]. The other hydrogen atoms were placed in calculated positions with and refined in the riding model with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
[Figure 2] Fig. 2. Crystal packing of the title compound with hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.
rac-Diethyl 6-hydroxy-4-[(2-hydroxyethyl)amino]-6-methyl-2-phenylcyclohex-3-ene-1,3- dicarboxylate top
Crystal data top
C21H29NO6F(000) = 1680
Mr = 391.45Dx = 1.245 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2594 reflections
a = 41.078 (14) Åθ = 2.4–30.1°
b = 5.940 (2) ŵ = 0.09 mm−1
c = 18.683 (6) ÅT = 100 K
β = 113.581 (13)°Prism, colourless
V = 4178 (2) Å30.30 × 0.30 × 0.30 mm
Z = 8
Data collection top
Bruker APEXII CCD
diffractometer		4530 independent reflections
Radiation source: fine-focus sealed tube3052 reflections with I > 2σ(I)
graphiteRint = 0.060
φ and ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)		h = −52→48
Tmin = 0.973, Tmax = 0.973k = −7→7
18275 measured reflectionsl = −23→23
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: difference Fourier map
wR(F2) = 0.143H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.070P)2 + 1.6P]
where P = (Fo2 + 2Fc2)/3
4530 reflections(Δ/σ)max < 0.001
263 parametersΔρmax = 0.27 e Å−3
8 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C21H29NO6V = 4178 (2) Å3
Mr = 391.45Z = 8
Monoclinic, C2/cMo Kα radiation
a = 41.078 (14) ŵ = 0.09 mm−1
b = 5.940 (2) ÅT = 100 K
c = 18.683 (6) Å0.30 × 0.30 × 0.30 mm
β = 113.581 (13)°
Data collection top
Bruker APEXII CCD
diffractometer		4530 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)		3052 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.973Rint = 0.060
18275 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.143Δρmax = 0.27 e Å−3
S = 1.00Δρmin = −0.25 e Å−3
4530 reflectionsAbsolute structure: ?
263 parametersFlack parameter: ?
8 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.45627 (3)0.6020 (2)0.27020 (7)0.0437 (3)
H1O0.45580.63890.22110.065*
O20.40537 (4)0.7311 (3)0.49029 (7)0.0610 (4)
O30.38193 (4)0.9619 (2)0.38680 (7)0.0524 (4)
O40.39044 (4)0.6792 (3)0.11937 (8)0.0648 (4)
O50.35176 (4)0.4026 (3)0.10896 (7)0.0627 (4)
O60.47333 (4)0.3324 (3)0.64070 (7)0.0546 (4)
H6O0.49840.34820.66840.082*
N10.44548 (4)0.3995 (3)0.47590 (8)0.0457 (4)
H1N0.43590.47760.50460.055*
C10.40713 (5)0.6258 (3)0.36860 (9)0.0373 (4)
C20.38927 (5)0.6718 (3)0.28057 (9)0.0375 (4)
H20.40050.80890.26900.045*
C30.39557 (5)0.4713 (3)0.23451 (9)0.0385 (4)
H30.38220.33880.24170.046*
C40.43481 (5)0.4067 (3)0.26514 (9)0.0390 (4)
C50.44550 (5)0.3190 (3)0.34878 (9)0.0399 (4)
H5A0.43690.16230.34610.048*
H5B0.47170.31500.37470.048*
C60.43160 (5)0.4552 (3)0.39896 (9)0.0368 (4)
C70.47043 (6)0.2210 (3)0.51284 (10)0.0471 (5)
H7A0.49490.27370.52460.056*
H7B0.46550.09050.47710.056*
C80.46723 (6)0.1506 (4)0.58791 (10)0.0506 (5)
H8A0.44320.08920.57530.061*
H8B0.48460.02950.61320.061*
C90.39840 (5)0.7687 (3)0.42100 (10)0.0424 (4)
C100.36501 (6)1.0945 (4)0.42722 (13)0.0575 (6)
H10A0.37041.25610.42460.069*
H10B0.37421.04960.48280.069*
C110.32549 (7)1.0567 (5)0.38929 (16)0.0751 (7)
H11A0.31381.15010.41520.113*
H11B0.32030.89770.39400.113*
H11C0.31671.09770.33390.113*
C120.34941 (5)0.7105 (3)0.24955 (10)0.0426 (4)
C130.32735 (6)0.5590 (4)0.26467 (13)0.0601 (6)
H130.33750.43440.29810.072*
C140.29093 (7)0.5856 (5)0.23212 (17)0.0806 (8)
H140.27630.47970.24330.097*
C150.27578 (7)0.7649 (6)0.18358 (16)0.0840 (8)
H150.25070.78300.16110.101*
C160.29710 (7)0.9171 (5)0.16787 (15)0.0774 (8)
H160.28681.04200.13480.093*
C170.33352 (6)0.8901 (4)0.19988 (12)0.0561 (5)
H170.34800.99550.18780.067*
C180.38008 (5)0.5315 (3)0.14896 (9)0.0448 (4)
C190.32971 (18)0.4777 (12)0.0292 (2)0.0852 (16)0.60
H19A0.34220.4503−0.00570.102*0.60
H19B0.32470.64080.02880.102*0.60
C200.29543 (14)0.3442 (11)0.0017 (4)0.090 (2)0.60
H20A0.28230.3655−0.05460.135*0.60
H20B0.28090.39660.02920.135*0.60
H20C0.30090.18410.01280.135*0.60
C19'0.3332 (3)0.440 (2)0.0253 (2)0.0852 (16)0.40
H19C0.33870.3178−0.00400.102*0.40
H19D0.34090.58490.01060.102*0.40
C20'0.2936 (2)0.446 (2)0.0062 (7)0.090 (2)0.40
H20D0.28050.4722−0.04990.135*0.40
H20E0.28850.56800.03560.135*0.40
H20F0.28630.30210.02060.135*0.40
C210.44184 (6)0.2255 (4)0.21482 (11)0.0509 (5)
H21A0.43790.28860.16350.076*
H21B0.42570.09840.20830.076*
H21C0.46650.17360.24040.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0424 (7)0.0596 (8)0.0284 (6)−0.0073 (6)0.0136 (5)0.0000 (5)
O20.0842 (11)0.0693 (10)0.0328 (7)0.0258 (8)0.0268 (7)0.0055 (7)
O30.0640 (9)0.0523 (8)0.0420 (7)0.0161 (7)0.0223 (7)0.0043 (6)
O40.0747 (11)0.0811 (11)0.0362 (7)−0.0125 (9)0.0197 (7)0.0125 (7)
O50.0593 (10)0.0871 (11)0.0297 (7)−0.0186 (8)0.0051 (6)−0.0025 (7)
O60.0460 (8)0.0852 (10)0.0295 (6)0.0036 (7)0.0118 (6)−0.0072 (7)
N10.0523 (10)0.0588 (10)0.0246 (7)0.0163 (8)0.0140 (7)0.0048 (7)
C10.0379 (10)0.0466 (10)0.0266 (8)0.0022 (8)0.0122 (7)0.0019 (7)
C20.0402 (10)0.0437 (9)0.0268 (7)−0.0006 (8)0.0114 (7)0.0038 (7)
C30.0416 (10)0.0462 (10)0.0258 (8)−0.0044 (8)0.0115 (7)0.0019 (7)
C40.0437 (11)0.0481 (10)0.0263 (8)−0.0017 (8)0.0152 (7)−0.0005 (7)
C50.0440 (11)0.0482 (10)0.0278 (8)0.0061 (8)0.0146 (7)0.0024 (7)
C60.0378 (10)0.0476 (10)0.0242 (7)−0.0014 (8)0.0115 (7)−0.0007 (7)
C70.0525 (12)0.0580 (12)0.0284 (8)0.0146 (9)0.0138 (8)0.0051 (8)
C80.0570 (13)0.0608 (12)0.0293 (9)0.0069 (10)0.0124 (8)0.0079 (8)
C90.0430 (11)0.0497 (10)0.0329 (8)0.0041 (9)0.0136 (8)0.0002 (8)
C100.0666 (15)0.0548 (12)0.0534 (12)0.0160 (11)0.0264 (11)0.0000 (10)
C110.0705 (17)0.0824 (17)0.0780 (16)0.0095 (14)0.0355 (14)−0.0034 (14)
C120.0402 (11)0.0537 (11)0.0306 (8)0.0018 (9)0.0106 (7)0.0046 (8)
C130.0475 (13)0.0747 (15)0.0566 (12)0.0020 (11)0.0193 (10)0.0196 (11)
C140.0495 (15)0.109 (2)0.0837 (18)−0.0089 (15)0.0269 (13)0.0163 (16)
C150.0408 (14)0.121 (2)0.0760 (17)0.0139 (15)0.0087 (12)0.0119 (17)
C160.0581 (16)0.0904 (19)0.0672 (15)0.0222 (14)0.0079 (12)0.0212 (14)
C170.0514 (13)0.0600 (13)0.0484 (11)0.0060 (10)0.0111 (10)0.0112 (10)
C180.0442 (11)0.0573 (11)0.0304 (8)−0.0019 (9)0.0122 (8)0.0004 (8)
C190.066 (2)0.145 (3)0.0269 (11)−0.014 (2)0.0000 (12)0.0007 (15)
C200.066 (2)0.125 (7)0.0596 (19)0.000 (3)0.0030 (16)0.003 (4)
C19'0.066 (2)0.145 (3)0.0269 (11)−0.014 (2)0.0000 (12)0.0007 (15)
C20'0.066 (2)0.125 (7)0.0596 (19)0.000 (3)0.0030 (16)0.003 (4)
C210.0642 (14)0.0573 (12)0.0362 (9)0.0049 (10)0.0253 (9)−0.0034 (9)
Geometric parameters (Å, °) top
O1—C41.437 (2)C10—C111.506 (3)
O1—H1O0.9360C10—H10A0.9900
O2—C91.229 (2)C10—H10B0.9900
O3—C91.356 (2)C11—H11A0.9800
O3—C101.447 (2)C11—H11B0.9800
O4—C181.202 (2)C11—H11C0.9800
O5—C181.343 (2)C12—C131.384 (3)
O5—C19'1.456 (3)C12—C171.393 (3)
O5—C191.470 (3)C13—C141.380 (3)
O6—C81.416 (2)C13—H130.9500
O6—H6O0.9543C14—C151.376 (4)
N1—C61.358 (2)C14—H140.9500
N1—C71.444 (2)C15—C161.370 (4)
N1—H1N0.9087C15—H150.9500
C1—C61.380 (3)C16—C171.381 (3)
C1—C91.445 (2)C16—H160.9500
C1—C21.534 (2)C17—H170.9500
C2—C121.520 (3)C19—C201.515 (3)
C2—C31.550 (2)C19—H19A0.9900
C2—H21.0000C19—H19B0.9900
C3—C181.508 (2)C20—H20A0.9800
C3—C41.528 (3)C20—H20B0.9800
C3—H31.0000C20—H20C0.9800
C4—C211.531 (2)C19'—C20'1.523 (3)
C4—C51.535 (2)C19'—H19C0.9900
C5—C61.512 (2)C19'—H19D0.9900
C5—H5A0.9900C20'—H20D0.9800
C5—H5B0.9900C20'—H20E0.9800
C7—C81.519 (2)C20'—H20F0.9800
C7—H7A0.9900C21—H21A0.9800
C7—H7B0.9900C21—H21B0.9800
C8—H8A0.9900C21—H21C0.9800
C8—H8B0.9900
C4—O1—H1O110.6C11—C10—H10A109.9
C9—O3—C10117.92 (15)O3—C10—H10B109.9
C18—O5—C19'118.3 (3)C11—C10—H10B109.9
C18—O5—C19115.9 (2)H10A—C10—H10B108.3
C19'—O5—C1911.3 (10)C10—C11—H11A109.5
C8—O6—H6O107.7C10—C11—H11B109.5
C6—N1—C7126.98 (15)H11A—C11—H11B109.5
C6—N1—H1N113.8C10—C11—H11C109.5
C7—N1—H1N119.0H11A—C11—H11C109.5
C6—C1—C9119.37 (15)H11B—C11—H11C109.5
C6—C1—C2121.94 (15)C13—C12—C17117.61 (19)
C9—C1—C2118.67 (15)C13—C12—C2121.15 (17)
C12—C2—C1114.57 (14)C17—C12—C2121.05 (17)
C12—C2—C3107.33 (14)C14—C13—C12121.2 (2)
C1—C2—C3110.10 (14)C14—C13—H13119.4
C12—C2—H2108.2C12—C13—H13119.4
C1—C2—H2108.2C15—C14—C13120.3 (2)
C3—C2—H2108.2C15—C14—H14119.9
C18—C3—C4113.02 (14)C13—C14—H14119.9
C18—C3—C2108.21 (15)C16—C15—C14119.5 (2)
C4—C3—C2111.72 (14)C16—C15—H15120.2
C18—C3—H3107.9C14—C15—H15120.2
C4—C3—H3107.9C15—C16—C17120.4 (2)
C2—C3—H3107.9C15—C16—H16119.8
O1—C4—C3110.45 (14)C17—C16—H16119.8
O1—C4—C21110.28 (14)C16—C17—C12121.0 (2)
C3—C4—C21112.11 (15)C16—C17—H17119.5
O1—C4—C5106.80 (14)C12—C17—H17119.5
C3—C4—C5107.19 (13)O4—C18—O5123.21 (15)
C21—C4—C5109.82 (15)O4—C18—C3125.72 (16)
C6—C5—C4115.09 (15)O5—C18—C3111.03 (16)
C6—C5—H5A108.5O5—C19—C20107.3 (3)
C4—C5—H5A108.5O5—C19—H19A110.3
C6—C5—H5B108.5C20—C19—H19A110.3
C4—C5—H5B108.5O5—C19—H19B110.3
H5A—C5—H5B107.5C20—C19—H19B110.3
N1—C6—C1122.83 (15)H19A—C19—H19B108.5
N1—C6—C5115.03 (15)O5—C19'—C20'107.8 (3)
C1—C6—C5122.12 (14)O5—C19'—H19C110.1
N1—C7—C8109.65 (15)C20'—C19'—H19C110.1
N1—C7—H7A109.7O5—C19'—H19D110.1
C8—C7—H7A109.7C20'—C19'—H19D110.1
N1—C7—H7B109.7H19C—C19'—H19D108.5
C8—C7—H7B109.7C19'—C20'—H20D109.5
H7A—C7—H7B108.2C19'—C20'—H20E109.5
O6—C8—C7112.12 (17)H20D—C20'—H20E109.5
O6—C8—H8A109.2C19'—C20'—H20F109.5
C7—C8—H8A109.2H20D—C20'—H20F109.5
O6—C8—H8B109.2H20E—C20'—H20F109.5
C7—C8—H8B109.2C4—C21—H21A109.5
H8A—C8—H8B107.9C4—C21—H21B109.5
O2—C9—O3120.81 (16)H21A—C21—H21B109.5
O2—C9—C1126.18 (17)C4—C21—H21C109.5
O3—C9—C1112.98 (15)H21A—C21—H21C109.5
O3—C10—C11109.02 (18)H21B—C21—H21C109.5
O3—C10—H10A109.9
C6—C1—C2—C12134.86 (18)C6—C1—C9—O2−14.7 (3)
C9—C1—C2—C12−46.3 (2)C2—C1—C9—O2166.41 (19)
C6—C1—C2—C313.8 (2)C6—C1—C9—O3163.31 (16)
C9—C1—C2—C3−167.34 (16)C2—C1—C9—O3−15.6 (2)
C12—C2—C3—C1859.04 (18)C9—O3—C10—C11−102.7 (2)
C1—C2—C3—C18−175.64 (14)C1—C2—C12—C13−52.1 (2)
C12—C2—C3—C4−175.91 (13)C3—C2—C12—C1370.5 (2)
C1—C2—C3—C4−50.59 (18)C1—C2—C12—C17133.07 (19)
C18—C3—C4—O171.70 (18)C3—C2—C12—C17−104.3 (2)
C2—C3—C4—O1−50.64 (17)C17—C12—C13—C14−0.4 (3)
C18—C3—C4—C21−51.7 (2)C2—C12—C13—C14−175.5 (2)
C2—C3—C4—C21−174.06 (14)C12—C13—C14—C150.0 (4)
C18—C3—C4—C5−172.31 (15)C13—C14—C15—C16−0.1 (4)
C2—C3—C4—C565.35 (18)C14—C15—C16—C170.6 (4)
O1—C4—C5—C675.18 (19)C15—C16—C17—C12−1.0 (4)
C3—C4—C5—C6−43.2 (2)C13—C12—C17—C160.9 (3)
C21—C4—C5—C6−165.23 (16)C2—C12—C17—C16175.9 (2)
C7—N1—C6—C1178.34 (19)C19'—O5—C18—O41.5 (8)
C7—N1—C6—C5−2.8 (3)C19—O5—C18—O4−11.0 (5)
C9—C1—C6—N16.8 (3)C19'—O5—C18—C3179.3 (7)
C2—C1—C6—N1−174.32 (17)C19—O5—C18—C3166.8 (5)
C9—C1—C6—C5−171.97 (17)C4—C3—C18—O4−58.8 (3)
C2—C1—C6—C56.9 (3)C2—C3—C18—O465.5 (3)
C4—C5—C6—N1−170.10 (16)C4—C3—C18—O5123.50 (18)
C4—C5—C6—C18.8 (3)C2—C3—C18—O5−112.22 (18)
C6—N1—C7—C8−156.00 (19)C18—O5—C19—C20−167.3 (4)
N1—C7—C8—O6−58.2 (2)C19'—O5—C19—C2088 (2)
C10—O3—C9—O2−15.2 (3)C18—O5—C19'—C20'−133.8 (6)
C10—O3—C9—C1166.70 (17)C19—O5—C19'—C20'−53 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6i0.941.922.802 (2)157
O1—H1O···O40.942.613.061 (2)110
O6—H6O···O1ii0.951.782.727 (2)172
N1—H1N···O20.911.912.650 (2)137
Symmetry codes: (i) x, −y+1, z−1/2; (ii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6i0.941.922.802 (2)157
O6—H6O···O1ii0.951.782.727 (2)172
N1—H1N···O20.911.912.650 (2)137
Symmetry codes: (i) x, −y+1, z−1/2; (ii) −x+1, −y+1, −z+1.
Acknowledgements top

We thank Professor Victor N. Khrustalev for fruitful discussions and help with this work.

references
References top

Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Krivenko, A. P., Kozlova, E. A., Grigorev, A. V. & Sorokin, V. V. (2003). Molecules, 8, 251–255

Sheldrick, G. M. (1998). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.